Porous monolithic microreactors show great promise in catalytic applications, but are usually based on non-renewable materials. Herein, we demonstrate a Ni/Au nanoparticle-decorated carbonized wood (Ni/Au-CW) monolithic membrane microreactor for the efficient reduction of 4-nitrophenol. The hierarchical porous wood structure supports uniformly distributed heterobimetallic Ni/Au nanoparticles. As a consequence of these two factors, both mass diffusion and electron transfer are enhanced, resulting in a superior reduction efficiency of 99.5% as the liquor flows through the optimised Ni/Au-CW membrane. The reaction mechanism was investi-gated by electron paramagnetic resonance spectroscopy and density functional theory calculations. The proposed attraction-repulsion mechanism facilitated by the bimetallic nanoparticles has been ascribed to the different electronegativities of Ni and Au. The Ni/Au-CW membrane exhibits excellent catalytic performance and could be to other transformations.